Non-Metal Tanning Process

ABSTRACT

Tanned leather, skin or pelt is produced by non-metal tanning, comprising the step of tanning a bated hide, skin or pelt with a tanning agent (A), the tanning agent (A) being at least one compound of formula (I), 
     
       
         
         
             
             
         
       
     
     wherein
     X signifies fluorine or chlorine, and/or ( + NR 3 ) 0-1 , wherein R is a substituted C 1  to C 6  alkyl group or an unsubstituted C 1  to C 6  alkyl group, an unsubstituted C 6  to C 10  aryl group or a substituted C 6  to C 10  aryl group or a C 5  to C 6  heteroaryl group.   R1 signifies hydrogen, C 1-8 -alkyl or an alkyleneoxy radical of formula (Ia),   

       —(—C 2-3  alkylene—O—) q —H  (Ia)
     R2 signifies hydrogen, hydroxy, C 1-4 -alkyl or C 1-4 -alkoxy,   m signifies 1 or 2,   n signifies 0 to 2,   q is of from 1 to 10,   M signifies hydrogen or an alkali metal cation or an ammonium cation, the ammonium cation being a protonated tertiary amine or a quaternary ammonium cation,
 
in a tanning bath, the tanning bath having a pH of from 6 to 10 at the beginning of tanning step, wherein the bated hide or skin or pelt is subjected to tanning with (A) without previous pickling.

In the production of leather, the tanning process is of decisiveimportance for the properties and quality of the resulting leather.Among the various tannings known in the art, i.e. mineral, vegetable andsynthetic, chrome-based tannage is a conventional and widely spread wayof tanning which is readily feasible in an industrial scale on mostvarious kinds of skins and hides, and provides tanned leathers withsatisfactory properties (such as high shrinkage temperatures T_(s),suppleness and suitability for subsequent processing such asneutralization, retanning, fat-liquoring, dyeing, finishing).

Chrome-based tanning agents and tannings are however consideredenvironmentally unfriendly and it is therefore desired to provide othertanning methods.

In WO 02/50313 A2 it has been proposed to add certain laccase derivedenzymes to the tanning bath with synthetic or vegetable tanning agentsand then to add an oxidising agent. This adds however some further stepin tanning and furthermore requires a particular precise control of theenzyme activity.

In WO 94/10345 A1 there is described a metal tanning in which in a firststep (a) the substrate is pre-treated with certain compounds of thethere defined formula (1) containing two substituents selected fromcarboxy and hydroxy, and a defined reactive group, and in a second step(b) a metal tannage is applied. Pre-treatment (a) is done in order toimprove tanning with metal tanning agents in subsequent step (b).

In an article by Evans et al. in J.A.L.C.A. Vol. 82 (1987) pages 88-95,mentioned in the introduction of WO 94/10345 A1 and which relates to apre-treatment of certain collagen substrates with 1,2-dicarboxylic acidsand subsequent aluminium tannage, there is described the treatment oflambskin with2-N-[bis-(3′,4′-dicarboxyphenyl)methyl]methylamino-4,6-dichloro-s.triazineand subsequent tannage with basified aluminium sulphate. Also in thisarticle the pre-treatment is done in order to improve tanning with themetal tanning agent (basified aluminium sulphate) in the subsequenttanning step.

J. H. Bowes and C. W. Cater in the article “Crosslinking of Collagen” inJ. Appl. Chem., 15, Jul., 1965, describe some crosslinking tests carriedout on collagen of denatured animal tendon (kangaroo tail tendon, KTT)with various crosslinking compounds—which need not act as completetanning materials in themselves—in particulardifluorodinitrodiphenylsulphone, diisocyanates, a number of aldehydes(formaldehyde, glyoxal, malonic dialdehyde, succinic dialdehyde,glutaraldehyde, adipic dialdehyde, acrolein and dialdehyde starch),cyanuric chloride and a number of cyanuric chloride derivatives (methoxyderivative, amino derivative hydrochloride, sulphonate derivative sodiumsalt, 5-sulphonaphth-1-ylamino derivative sodium salt, andbis-4,4′-diaminostilbene-2,2′-disulphonic acid derivative sodiumsalt)—in order to assess their crosslinking potentiality, and whichcould be combined with conventional tanning materials for improvingresistance to deterioration due to moist heat and perspiration. Fromtheir measurements, finally, they conclude that aldehydes(glutaraldehyde) appear to be most promising because of number ofcrosslinks and stability, whereas cyanuric chloride derivatives would beless useful as crosslinking agents in collagen.

It has now surprisingly been found that a non-metal tanning ofoutstanding quality can be achieved using the below defined tanningagents—in particular even as complete tanning materials—and tanningmethods, which also allow to omit a pickling as conventionally carriedout before chrome tanning or aldehyde tanning, unless necessary forother reasons e.g. for degreasing. The invention relates to the tanningprocess, the defined tanning agent compositions, the use of the tanningagents and their compositions, the tanned leather, skin or pelt and itsuse for further processing.

As a non-metal tanning process there is meant herein a tanning producedwithout using any cationic metal compounds which have tanning activity,i.e. polybasic metal compounds, mainly chromium, aluminium, iron,zirconium or titanium salts etc. As a non-metal tanning agent there ismeant herein a tanning agent that does not comprise any cationic metalcompounds of tanning activity, i.e. polybasic metal compounds, mainlychromium, aluminium, iron, zirconium or titanium salts, etc.

In the following, alkyl means linear or branched alkyl, if not otherwisestated.

The invention thus firstly provides a process for the production oftanned leather, skins or pelts by non-metal tanning, comprising the stepof tanning a bated hide, skin or pelt with a tanning agent (A), thetanning agent (A) being at least one compound of formula (I),

wherein

-   X signifies fluorine or chlorine, and/or (⁺NR₃)₀₋₁, wherein R is a    substituted C₁ to C₆ alkyl group or an unsubstituted C₁ to C₆ alkyl    group, an unsubstituted C₆ to C₁₀ aryl group or a substituted C₆ to    C₁₀ aryl group or a C₅ to C₆ heteroaryl group.-   R1 signifies hydrogen, C₁₋₈-alkyl or an alkyleneoxy radical of    formula (Ia),

—(—C₂₋₃ alkylene—O—)_(q)—H  (Ia)

-   R2 signifies hydrogen, hydroxy, C₁₋₄-alkyl or C₁₋₄-alkoxy,-   m signifies 1 or 2,-   n signifies 0 to 2,-   q is of from 1 to 10,-   M signifies hydrogen or an alkali metal cation or an ammonium    cation, the ammonium cation being a protonated tertiary amine or a    quaternary ammonium cation,    in a tanning bath, the tanning bath having a pH of from 6 to 10 at    the beginning of tanning step, wherein the bated hide or skin or    pelt is subjected to tanning with (A) without previous pickling.

The tanning agent (A) may consist of more than one compound of formula(I). In case of the tanning agent (A) containing a radical of formula(Ia) it may be a mixture of compounds of formula (I), in which q mayalso be calculated and expressed as an average number of alkyleneoxyunits in the alkyleneoxy radical of formula (Ia) per compound of formula(I), based on all radicals of the formula (Ia) in the mixture.Preferably, the tanning agent (A) is only one compound of formula (I),in case that R1 is not the radical of the formula (Ia). In case, that R1is the radical of the formula (Ia), the tanning agent (A) may alsocomprise compounds of formula (I) with a distribution of chain lengthsof the radical of the formula (Ia).

X preferably signifies chlorine or fluorine. More preferably X signifieschlorine.

In case of q being of from 2 to 10, the alkylenoxy radical of formula(Ia) can also comprise a mixture of both ethylenoxy units andpropylenoxy units.

If q is of from 2 to 10, then the radical of formula (Ia) preferablycontains at least two ethyleneoxy units.

In case of compounds of formula (I) with q>5, preferably at least 40% ofthe total number of alkyleneoxy units in the radical of formula (Ia) areethyleneoxy.

In case that the tanning agent (A) is a mixture of two or more compoundsof formula (I) with R1 in these compounds of formula (I) beingalkylenoxy radicals of formula (Ia), preferably the average q ofalkylenoxy units per compound of formula (I) in the mixture is of from1.0 to 10.0.

Any propylene in the alkyleneoxy radical of formula (Ia) is preferably apropylene-1,2.

R1 signifies preferably hydrogen or C₁₋₄-alkyl.

More preferably R1 is selected from the group consisting of hydrogen,methyl or ethyl.

R2 signifies preferably hydrogen, hydroxy-, methyl- or methoxy-group.

If m is 1, then the carboxy group is ortho-, meta- or para-position,with respect to the amino group —N(R1)— in formula (I). If m signifies2, then the two carboxy groups are preferably in the positions 3 and 5,or 3 and 4.

n signifies preferably 0 to 1.

Where M is an alkali metal cation or a ammonium cation, then it may beany alkali metal cation or an ammonium cation as conventionally employedfor salt formation in anionic compounds.

Preferably, the alkali metal cation is selected from the groupconsisting of lithium, sodium and potassium, more preferably the alkalimetal cation is sodium. Preferably, the ammonium cation is a cation offormula (Ib),

wherein

-   R10, R11, R12 and R13 are same or different and independently from    each other selected from the group consisting of H, C₁₋₄-alkyl,    C₂₋₃-hydroxyalkyl and benzyl, with the proviso, that only one of the    four substituents R10, R11, R12 and R13 may be H.

Preferably,

-   R10 is H or C₁₋₄-alkyl, and-   R11, R12 and R13 are same or different and independently from each    other selected from the group consisting of C₁₋₄-alkyl,    C₂₋₃-hydroxyalkyl; or-   R10, R11, R12 and R13 are same or different and independently from    each other are C₁₋₄-alkyl; or-   R10, R11 and R12 are same or different and independently from each    other are C₁₋₄-alkyl or C₂₋₃-hydroxyalkyl, and-   R13 is benzyl.

More preferably, the ammonium cation is selected from the groupconsisting of monohydrogen-tri(C₂₋₃-alkanol)-ammonium,tetra(C₁₋₄-alkyl)-ammonium, tri(C₁₋₄-alkyl)-mono(C₂₋₃-alkanol)-ammonium,di(C₂₋₃-alkanol)-di(C₁₋₄-alkyl)-ammonium,mono(C₁₋₄-alkyl)-tri(C₂₋₃-alkanol)-ammonium,monobenzyl-tri(C₁₋₄-alkyl)-ammonium andmonobenzyl-tri(C₂₋₃-alkanol)-ammonium.

Especially, the ammonium cation is a quaternary ammonium cation.

More especially preferably, M is an alkali metal cation, even moreespecially preferably M is sodium.

Preferably, compound of formula (I) is a compound of formula (I-I),

more preferably a compound of formula (I-II).

The compounds of formula (I) are known or may be produced according toknown methods, preferably by reaction of a compound of formula (II),

with a compound of formula (III),

with X, R1, R2, m, n and M having the definition as given above, alsowith all their preferred embodiments.

The compounds of formula (III) are commercially available or may beproduced according to known methods from known starting materials.Compounds of formula (III) with R1 not being H, may e.g. be produced byalkylation reaction of a compound of formula (IIIa)

by an alkylation reaction with an alkylating agent suitable for theintroduction of the residue R1, e.g. a respective chloride or epoxide.If suitable the alkylation is done with intermediate protection of oneof the two hydrogens connected to the nitrogen in formula (IIIa) byacetylation and subsequent hydrolysis after the alkylation reaction ofthe resulting acetylamino group.

The reaction of the compounds of formula (II) with the compounds offormula (III) is a reaction which splits off an acid H—X.

The reaction of the compound of formula (II) with the compound offormula (III) may be carried out in an aqueous, aqueous/organic ororganic medium. Preferably, an aqueous solution or dispersion ofcompound of formula (III) is mixed with the compound of formula (II).The compound of formula (II) is preferably in form of a dry compound, anorganic solution or dispersion or an aqueous dispersion. Preferably, anaqueous solution or dispersion of compound of formula (III) is added toan aqueous dispersion of compound of formula (II). In another preferredembodiment, the dry compound of formula (II) is stirred into apreferably aqueous solution or dispersion of compound of formula (III).The reaction is preferably carried out in the presence of a base orother reactant suitable for binding the acid H—X.

Suitable organic media include e.g. ethanol, isopropanol, acetone,methylethylketone, dimethylsulphoxide, chloroform, chlorobenzene andtoluene. Preferably the reaction is carried out in aqueous medium.

Preferably, 1.00±0.05 mol of compound of formula (II) per mol ofcompound of formula (III) is used.

The concentration of compound of formula (II) is e.g. of from 2 to 70%by weight, preferably 5 to 50% by weight, the % by weight being based onthe total weight of the reaction mixture comprising compound of formula(II), (III) and the aqueous, aqueous/organic or organic medium.

When the compound of formula (II) is dissolved in an organic medium, itsconcentration is preferably high, in particular close to saturation inorder to reduce to a minimum the amount of solvent to be evaporated uponcompletion of the reaction.

Dispersion of compound of formula (II) or of compound of formula (III),preferably for dispersion in water, may be brought about by plainstirring or also by the use of a suitable surfactant (B) acting as adispersing agent.

For dispersing a compound of formula (II) or a compound of formula(III), wherein the sulfonic acid group of compound of formula (III) isin protonated form, preferably for dispersing in water, surfactant (B)may be employed in a suitable efficient concentration, e.g. in a weightratio of surfactant (B) to the compound of formula (II) or to thecompound of formula (III) preferably of from 0.002 to 2, more preferablyof from 0.004 and 1, even more preferably of from 0.005 and 0.5.

The compounds of formula (III) may be used in salt form, the salt formbeing preferably an alkali metal salt of the sulfonic acid, morepreferably a sodium salt. The compounds of formula (III) in salt formare in general soluble in water and they are suitably employed in theform of an aqueous solution or dispersion (at concentrations higher thanthe one corresponding to the saturated solution), preferably in anamount of from 2 to 70% by weight, more preferably 10 to 50% by weight,the % weight being based on the total weight of the solution ordispersion of compound of formula (III). Preferably this solution ordispersion contains also a dispersing agent (B) as mentioned above, in aconcentration as mentioned above suitable for dispersing compound offormula (II) when the latter is added as a dry product and is stirredinto the solution.

According to a preferred embodiment, a compound of formula (II) isstirred into an aqueous solution of a compound of formula (III)containing a surfactant (B).

Where R1 is a radical of formula (Ia) with q being of from 2 to 10, theamount of surfactant (B) may be reduced or the use of surfactant (B) mayeven be omitted.

The surfactant (B) is preferably selected from the group consisting of

-   (B1) non-ionic surfactant,-   (B2) anionic surfactant,-   (B3) cationic surfactant,-   (B4) amphoteric surfactant and-   mixtures of two or more thereof,    with the proviso that the surfactant (B) does not have a substituent    capable of reacting with the compound of formula (II) under the    chosen reaction conditions, in particular does not have a primary or    secondary amino group. Preferable mixtures are mixtures of (B2) with    (B1) and/or (B4), of (B3) with (B1) and/or (B4) or of (B1) with    (B4).

Preferably, the non-ionic surfactant (B1) is selected from the groupconsisting of oligo- or polyglycolethers of aliphatic alcohols, oligo-or polyglycolesters of aliphatic carboxylic acids, oxyalkylated fattyacid amides and oxyalkylated partial esters of glycerol or sorbitol withfatty acids.

Preferably, the oxyalkylation of the fatty acid amides and theoxyalkylation of the partial esters of glycerol or sorbitol with fattyacids leads to oligo- or polyglycolether chains.

Preferably any oligo- or polyglycolether chain contains 2 to 60, morepreferably 2 to 24 oxyalkylene units which are oxyethylene andoptionally oxypropylene units, and preferably at least 40 mol-%, morepreferably at least 50 mol-% being oxyethylene units and preferably, thenon-ionic surfactant (B1) contains at least two oxyethylene units.

Preferably, the lipophilic aliphatic radical in the aliphatic alcohol,aliphatic carboxylic acids, fatty acid amides and fatty acids contain 8to 24 carbon atoms.

The aliphatic radical may be saturated or unsaturated (preferably itcontains only one double bond) and may be linear or branched, thebranched preferably saturated.

As examples of aliphatic alcohols there may be mentioned lauryl, cetyl,myristyl, stearyl or oleyl alcohol, and C₉₋₁₅-oxoalcohols.

As examples of aliphatic carboxylic acids and of fatty acids amidesthere may be mentioned lauric, palmitic, myristic, stearic, behenic,arachic or oleic acid or amide.

The oligo- or polyglycolethers of aliphatic alcohols may be produced byoxyethylation and, if oxypropylene units are also to be present,oxypropylation of the corresponding aliphatic alcohols.

The oxyalkylated fatty acid amides may be produced e.g. byoxyethylation, and if oxypropylene units are also to be present, byoxypropylation of the corresponding fatty acid amides, e.g. of aliphaticacid diethanolamide or diisopropanolamide.

Oligo- or polyglycolesters and sorbitol monoesters may e.g. be producedby esterification of a corresponding oligo- or poly-ethylene- andoptionally -propylene-glycolether or sorbitol. Monoglycerides may bepartial saponification products of corresponding naturally occurringtriglycerides.

Preferably, the anionic surfactant (B2) is selected from the groupconsisting of anionic polycarboxylates, aliphatic fatty acids in saltform (soaps), methyltaurides of aliphatic fatty acids and anionicderivatives of non-ionic surfactants, preferably of non-ionicsurfactants (B1), in particular carboxymethylation products orcarboxyethylation products of non-ionic surfactants (B1) or sulphuricacid monoesters or phosphoric acids monoesters of non-ionic surfactants(B1), in particular in alkali metal salt form.

Preferred anionic polycarboxylates are polyacrylates andpolymethacrylates.

Preferably, the cationic surfactant (B3) is selected from the groupconsisting of tertiary or preferably quaternary derivatives of fattyamines, e.g. with 8 to 24 carbon atoms in the fatty amine chain, and inwhich the substituents of the tertiary amino group or quaternaryammonium group are C₁₋₄ alkyl (preferably methyl or ethyl) orhydroxyl-C₁₋₄-alkyl (preferably ethanol or isopropanol) and optionallybenzyl, and where, if desired, the tertiary amino group or quaternaryammonium group may also contain an oligo- or polyglycolether chainanalogously as mentioned above in the non-ionic surfactants (B1). Asexamples of fatty amines there may be mentioned lauryl, cetyl, myristyl,stearyl or oleyl amine and the amino group may be substituted with twomethyl or ethyl groups and optionally a methyl or benzyl group, or withthree methyl or ethyl groups or with two ethanol groups. If the tertiaryamino group or quaternary ammonium group is oxyalkylated it maypreferably contain a total of 2 to 40, more preferably 2 to 24alkylenoxy groups, preferably at least 40 mol-% of which are ethyleneoxyand the remaining are propylenoxy. Tertiary amino groups are preferablyprotonated e.g. with hydrochloric, phosphoric or C₂₋₂₀-, preferablyC₂₋₅-alkanoic acid.

Preferably, the amphoteric surfactants (B4) are anionic derivatives of(B3), e.g. carboxymethylation products of (B3), carboxyethylationproducts of (B3), sulphuric or sulphamic acid monoesters of (B3), orphosphoric acid mono- or diesters of (B3) of those cationic surfactants(B3) containing a hydroxy group, betaines and sulphobetaines.

Preferably, the surfactant (B) is a non-ionic surfactant (B1).

Preferably—in particular if in formula (I) R1 signifieshydrogen—non-ionic surfactants (B1) are used, more preferably thenon-ionic surfactants (B1) are compounds of formula (IV)(polyglycolethers),

R3—O—(X—O)_(r)—H  (IV)

wherein

-   R3 signifies C₈₋₂₄-alkyl or C₈₋₂₄-alkenyl,-   X is selected from the group consisting of —CH₂—CH₂—, —CH₂—CH(CH₃)—,    —CH(CH₃)—CH₂— and combinations thereof, preferably of —CH₂—CH₂—,    —CH₂—CH(CH₃)— and combinations thereof,-   r signifies 2 to 60,    in case that the non-ionic surfactant (B1) of formula (IV) consists    of more than one compound of formula (IV), r may also be calculated    and expressed as the average number of radicals of the formula (IV)    in the mixture,    with the proviso that the compound of formula (IV) contains at least    two ethyleneoxy units, and with the proviso that at least 40% of the    total number of alkyleneoxy units in the compound of formula (IV)    are ethyleneoxy.

The reaction of the compound of formula (II) with the compound offormula (III) is preferably done at a temperature below 40° C., morepreferably of from −10 to 40° C., even more preferably of from −10 to+25° C., especially preferably of from 0 to 15° C.

Preferably, the reaction of the compound of formula (II) with thecompound of formula (III) is carried out under acidic to neutral pHconditions, more preferably at a pH of from 2 to 7, even more preferablyunder acidic conditions, especially preferably at a pH of from 2.5 to 6.

The base or other reactant which can be used for binding the acid H—Xand which can be used for pH adjustment during the reaction of thecompound of formula (II) with the compound of formula (III), ispreferably selected from the group consisting of alkali metal base,quaternary ammonium hydroxide and carbonate.

The alkali metal base is preferably selected from the group consistingof hydroxide, carbonate and bicarbonate of lithium, sodium and potassiumand mixtures thereof.

The quaternary ammonium hydroxide and carbonate is preferably selectedfrom the group consisting of hydroxide and carbonate oftetramethyl-ammonium, tetraethyl-ammonium and benzyl-trimethyl-ammonium.

If an organic solvent has been used, this may be eliminated byevaporation and, if desired, the resulting product may be dissolved ordispersed in water. If a dry product is desired, this may be obtainedfrom an aqueous solution or dispersion of the reaction product in amanner conventional per se, e.g. by precipitation (e.g. by salting out)and filtration, or by evaporation under controlled conditions.

A tanning agent (A) comprising more the one compound of formula (I) canbe produced by using more than one compound of formula (III) in thereaction of compound of formula (II) with compound of formula (III), orby physical mixing the compounds of formula (I). The physical mixing canbe done in dry form and/or in dissolved or dispersed form, preferably indissolved or dispersed form in water.

The tanning agent (A) may be used as such, as produced, preferably indry form or more preferably in the form of an aqueous solution ordispersion.

According to a particular aspect of the invention, the tanning agent (A)is in the form of an aqueous composition (T) which is free of anymetal-based compounds which have tanning activity, aqueous composition(T) comprising the tanning agent (A) and water, and preferably comprisesin addition the surfactant (B). Therefore, another subject of theinvention is a tanning process as described above, also with all itspreferred embodiments, wherein the tanning agent (A) is employed in theform of an aqueous composition (T) which is free of metal compounds oftanning activity.

More preferably, the composition (T) comprises of from 2 to 70% byweight, especially 10 to 50% by weight, the % by weight based on thetotal weight of the composition (T), of tanning agent (A).

Where surfactant (B) is present in the composition (T), the weight ratioof surfactant (B) to tanning agent (A) in the composition (T) ispreferably of from 0.001 to 1, more preferably of from 0.002 to 0.4,even more preferably of from 0.005 to 0.1.

Preferably, in the composition (T), the surfactant (B) is the non-ionicsurfactant (B1). If an anionic, cationic or amphoteric surfactant (B2),(B3) or (B4) is used, its amount is preferably of from 0.001 to 10mol-%, the mol-% with respect to the total molar amount of tanning agent(A). More preferably the surfactant (B) is only the non-ionic surfactant(B1). If surfactant (B2) is a polycarboxylate, its amount is preferably<5% by weight, more preferably of from 0.01 to 4% by weight, even morepreferably from 0.05 to 2% by weight, the % by weight being always basedon the total weight of tanning agent (A).

The composition (T) has preferably an acidic to neutral pH, morepreferably it has an acidic pH. For pH adjustment, a suitable buffer maybe employed and composition (T) thus preferably further comprises abuffer (C1) to keep an acidic to neutral pH, preferably to keep anacidic pH, more preferably to keep a pH of from 1 to 7, even morepreferably to keep a pH of from 1 to 5.

The buffer (C1) is preferably selected from the group consisting ofphthalate, oxalate and citrate of sodium and/or of potassium, mono- anddi-hydrogenphosphate of sodium and/or of potassium, mixture ofphosphoric acid and di-hydrogenphosphate of sodium and/or potassium andmixtures thereof, preferably a combination of KH₂PO₄ or NaH₂PO₄ andNa₂HPO₄ or K₂HPO₄.

The amount of buffer (C1) in the composition (T) is preferably chosen soas to achieve the desired pH mentioned above. The amount of buffer (C1)is preferably of from 0.1 to 5% by weight, the % by weight being basedon the total weight of the composition (T).

Compositions (T) advantageously may further comprise an agent (D) toprotect against the damaging action of microorganisms, preferably, agent(D) is a bacteriostatic additive and/or a microbicide, e.g. a fungicide.

As agent (D) there may be employed commercially available products,which may be employed in small concentrations, in particular accordingto the commercially recommended ones. The amount of of agent (D) in thecomposition (T) is preferably of from 0 to 10% by weight, morepreferably of from 0.01 to 10% by weight, even more preferably of from0.02 to 1% by weight, the % by weight being based on the total weight ofthe composition (T).

According to a particular further feature of the invention, aqueouscompositions (T) may further comprise a polysaccharide- based thickener(E).

As thickener (E) there may be employed products known per se, inparticular gums, carbohydrates, carbohydrate derivatives, e.g. pectinsand hydrophilic cellulose derivatives, which with water form viscoussolutions (colloidal or true solutions). There may be mentioned gums asobtainable by fermentation and optionally chemical modification ofnatural plant-exudates, e.g. xanthan gum, tragacanth gum, guar gum,carrageenan gum, alginate gum, agar gum, gum ghatti, and water solublecarbohydrate derivatives in particular pectins, e.g. pectins from fruits(e.g. citric fruits or apples) and amylopectins (e.g. from corn starchor potato starch), and hydroxyethylcellulose. The gums, carbohydratesand carbohydrate derivatives may also be chemically modified, providedthat they do not contain any substituents capable of reacting withtanning agent (A) under storage or application conditions, in particularthey do not contain any basic amino groups, especially any primary orsecondary amino groups.

Thickener (E) may be employed in a minor proportion in the composition(T), in particular as suffices for adjusting the viscosity of (T) sothat it is still flowable. Where thickener (E) is employed in thecomposition (T), it is added preferably in such a concentration that theviscosity of the composition (T) at 20° C. is preferably ≦10,000 mPa·s ,more preferably of from 200 to 10,000 mPa·s, even more preferably offrom 300 to 2,500 mPa·s, especially preferably 600 to 1,500 mPa·s. Theviscosity is the Brookfield rotational viscosity, spindle no. 3, 20 rpm.

Preferably the amount of thickener (E) in the composition (T) is of from0 to 5% by weight, more preferably of from 0.1 to 5% by weight, the % byweight based on the total weight of the composition (T).

Preferred compositions (T) are compositions (T1) comprising, in additionto the tanning agent (A), surfactant (B) and/or buffer (C1), morepreferably surfactant (B) or surfactant (B) and buffer (C1); preferablycompositions (T1) further comprise an agent (D) and/or a thickener (E).

Therefore, another preferred embodiment of the invention is a tanningprocess as described above, also with all its preferred embodiments,wherein the composition (T) is an aqueous composition (T1) comprisingthe tanning agent (A) and further comprising a surfactant (B) and/or abuffer (C₁) to keep an acidic to neutral pH.

Therefore, another preferred embodiment of the invention is a tanningprocess as described above, also with all its preferred embodiments,wherein the composition (T) is an aqueous composition (T1) of a tanningagent (A) comprising a surfactant (B) and/or a buffer (C₁) and furthercomprising an agent (D) to protect against the damaging action ofmicroorganisms and/or a polysaccharide-based thickener (E).

Preferably, the composition (T) is a composition (T1) comprising

of from 2 to 70% by weight, preferably 10-50% by weight, of tanningagent (A), the % by weight based on the total weight of the composition(T1);surfactant (B) in a weight ratio of surfactant (B) to tanning agent (A)of from 0.001 to 1, more preferably of from 0.002 to 0.4, even morepreferably of from 0.005 to 0.1;buffer (C1) in such an amount as to achieve a pH in the composition (T1)of from 1 to 7, more preferably pH 1 to 5, preferably the amount ofbuffer (C1) is of from 0.1 to 5% by weight, the % by weight being basedon the total weight of the composition (T1);of from 0 to 10% by weight, preferably of from 0.01 to 10% by weight,more preferably of from 0.02 to 1% by weight, of agent (D), the % byweight based on the total weight of the composition (T1),thickener (E) in such an amount that the viscosity of the composition(T1) at 20° C. (Brookfield rotational viscosity measured with spindleno. 3, 20 rpm) is ≦10,000 mPa·s, preferably of from 200 to 10,000 mPa·s,more preferably of from 300 to 2,500 mPa·s, even more preferably 600 to1,500 mPa·s, especially thickener (E) is used in an amount of from 0 to5%, more preferably of from 0.1 to 5% by weight, the % by weight basedon the total weight of the composition (T1);and the dry substance content of the composition (T1) is preferably offrom 4 to 75% by weight, more preferably in the range of 10 to 60% byweight, the % by weight based on the total weight of the composition(T1).

The dry substance content of (T) or (T1) may be assessed in a mannerconventional per se, e.g. by calculation based on the employed reactantsand components—mostly by simple addition of the amounts of thesubstances (expressed in dry form) added for the production of (T) or(T1) and substracting any water formed during the reaction-, or, whichis the preferable way, by substracting the water content determined in aconventional way, e.g. by titration, e.g. Karl Fischer titration, fromthe total weight of (T) or (T1).

Particularly preferably, composition (T) or (T1) is a composition (T2)which contains the thickener (E), preferably in an amount of 0.1% byweight, more preferably of from 0.1 to 5% by weight of (E), the % byweight based on the total weight of the composition (T2). The viscosityof the composition (T2) at 20° C. (Brookfield rotational viscositymeasured with spindle no. 3, 20 rpm) is preferably in the range of 300to 2,500 mPa·s, more preferably 600 to 1,500 mPa·s.

This composition (T2) is of satisfactory stability and is suitable forstorage and shipment and is directly usable. It is readily dilutablewith water and may be directly metered into the tanning drum, ifdesired.

As a substrate for the treatment with tanning agent (A), in particularfor tanning, there may be used any conventional animal hides, skins andpelts as are in general employed for tanning, e.g. hides from cow, calfor buffalo (e.g. also as split hides), skins from goat, sheep or pig,buckskins and pelts; but also other hides and skins e.g. from othermammals (foal, camel, lama, kangaroo, wallaroo, wallaby), reptiles(snakes, lizards), fishes (shark) or birds (ostrich), woolled skins andfurskins, may be used in the process of the invention.

The bated substrates (animal hides, skins or pelts) may have beenprocessed in the beamhouse before tanning, i.e. trimmed, soaked, limed,delimed and bated in conventional way. Before deliming the limed hides,skins or pelts are usually fleshed and, if required, split andoptionally scudded, shaved etc. and, if required, defatted and/ordehaired.

Bated hides, skins and pelts to be used as substrates in the process ofthe invention may have been produced in conventional way, in thebeamhouse, in particular by deliming the limed substrates and bating,using known agents for each of the mentioned processing steps.

Deliming may have been carried out in conventional way with knowncompounds such as acids, ammonium salts of low molecular aliphaticcarboxylic acids, ammonium sulphate or sodium phosphate. Optionally thedeliming composition may contain an enzyme e.g. as mentioned below, sothat, if desired, bating and deliming may at least in part be combined.

For bating there may be employed known proteolytic bates, in particularin the form of bating compositions based on conventional proteolyticenzymes, mainly bacterial proteases, fungal proteases, and pancreasenzyme. Occasionally also other enzymes may be employed, such aslipases, amylases and also other hydrolases. Pancreas enzyme alone or inadmixture with other enzymes (e.g. lipases, amylases and also otherhydrolases) is preferred. Commercial forms of such enzymes may beformulated together with other components, especially with some mineralcarriers, saccharides or polysaccharides and/or a hydrotrope. For thepurpose of the invention substrates conventionally bated with batingcompositions based on pancreas enzyme are well suitable.

The above bating compositions are in particular of an optimum activityin the weakly basic pH range, more particularly at a basic pH≦11, andconsequently the pH of the bated substrate is preferably in the weaklybasic range, in particular a pH in the range of 7.5 to 11, morepreferably 7.5 to 10.

Where the substrate has been delimed with acids, also acidic bates maybe used, e.g. pepsins e.g. in the form of a solution of 2% pepsin inwater and at a pH in the range of 3-4.

The tanning process of the invention is based on a true tanning with thetanning agent (A) leading to leathers, skins and pelts withcharacteristic true tannage properties, such as a reduction orelimination of swellability, reduction of deformability and augmentationof firmness, diminution of shrinkage in volume, surface and thickness bydrying, and increment of the porosity of the fibre texture, and furtherrising of shrinkage temperature and fastness of the collagen fibre tohot water, and of being non-rotting.

As a “step” in the tanning process according to the invention there ismeant any tanning step in a tanning process in which the tanning agent(A) acts on the non-tanned or not fully tanned substrate, i.e.pre-tanning, main tanning, or full or complete tanning (including also acombined tanning). The tanning agent (A) can thus be employed forpre-tanning, for main tanning, or for full (i.e. complete) tanning orfor both pre-tanning and main tanning, and for combined tannings. Theuse of the tanning agent (A) as a full tanning agent or as both apre-tanning agent and a main tanning agent is however the most relevantaspect of the invention.

The tanning process of the invention—which may be a one stage tanning,i.e. a full tanning, or a two stage tanning, i.e. a pre-tanning followedby a main tanning, or a combined tanning—can be carried out directlyafter bating.

The tanning process with the tanning agent (A) of the invention may becarried out in an aqueous, aqueous/organic or organic medium; suitableorganic media include e.g. ethanol, isopropanol, acetone,methylethylketone, dimethylsulphoxide, chloroform, chlorobenzene andtoluene. Preferably it is carried out in an aqueous bath, e.g. at a bathlength of 30 to 400% by weight of water, preferably 40 to 200%, mostpreferably 40 to 100%, the % by weight based on the weight of thefleshed or (if the hide has been split) the split substrate, and attemperatures preferably of from 10 to 50° C., more preferably of from 10to 40° C., even more preferably of from 15 to 40° C. Preferably tanningis begun at a temperature of from 10 to 35° C., more preferably of from15 to 30° C., and at the end the temperature is allowed to raisepreferably by 5 to 20 degrees, more preferably by 8 to 15 degrees, to anend temperature of from 20 to 40° C., preferably of from 25 to 40° C.

For the tanning process of the invention the tanning agent (A) is addedin the tanning bath in an efficient concentration, preferably of from0.5 to 20% by weight, more preferably of from 1 to 10% by weight, the %by weight being based on the weight of the fleshed or split substrate.The tanning agent (A) may be added in dry form or preferably in the formof an aqueous composition, preferably as mentioned above as acomposition (T).

With particular preference a surfactant, in particular as mentionedabove a surfactant (B), preferably a non-ionic surfactant (B1), and/or abuffer (C2) for nearly neutral to basic pH values, in particular pH 6,may be added in the tanning bath, in a weight ratio as suitable in orderto achieve the desired pH at the beginning of the tanning step.

Therefore, another preferred aspect of the invention is a tanningprocess as described above, also with all its preferred embodiments,wherein the tanning bath comprises a buffer (C2) to achieve a nearlyneutral to basic pH at the beginning of the tanning step.

As buffers (C2) there may be employed known buffers, preferably selectedfrom the group consisting of sodium and/or of potassium bicarbonate,sodium and/or of potassium carbonate, sodium and/or of potassiumhydrogen phosphate, sodium borate and trishydroxymethylaminomethane.Preferably buffer (C2) is a combination of KH₂PO₄ or NaH₂PO₄ and K₂HPO₄or Na₂HPO₄. For the tanning process of the invention it is of particularadvantage to employ compositions (T) as described above, whichpreferably already contain a surfactant (B) and optionally also agent(D) and/or thickener (E). The buffer (C2) may be added directly into thetanning bath. Preferably the buffer (C2) is added in a two-stage tanningbefore the main tanning step in order to set the pH of the main tanningbath. Compositions (T), in particular compositions (T1), are readilyefficient for tanning. The composition may contain some salt asresulting as a by-product from the synthesis of the compound of formula(I) from the reaction of compound of formula (II) with compound offormula (III).

The tanning process of the invention is started at a pH of from 6 to 10,preferably of from 6 to 9, more preferably of from 6.5 to 8.5, inparticular as suitable for inducing the reaction of tanning agent (A)with the substrate.

During the tanning, the pH gradually decreases spontaneously by a few pHunits, in particular by from 1 to 4 pH units, to a pH in the nearlyneutral to weakly acidic pH range, in particular to a pH of from 7 to3.5, preferably of from 6.5 to 3.5. The process may thus be carried outunder self-regulating pH conditions. If desired, however, the tanningreaction may be influenced by the addition of a minor proportion of acid(e.g. a mineral acid, e.g. sulphuric or phosphoric acid, or a lowmolecular carboxylic acid e.g. with 1 to 4, preferably 1 or 2, carbonatoms, e.g. formic or acetic acid), or by the addition of a minorproportion of base (alkali), e.g. in order to accelerate or deceleratethe reaction and/or to shift the pH slightly towards more neutralvalues.

In the process of the invention pickling is not necessary and isomitted. Therefore, subject of the invention is a tanning process asdescribed above, also in all its preferred embodiments, wherein thebated hide or skin or pelt is subjected to tanning with a tanning agent(A) without previous pickling.

If the tanning process is started at nearly neutral conditions, inparticular at a pH in the range of 6 to 7.5, the pH may initially alsobe kept in this range or increased, to give a pH in the range of 6 to 9,by addition of a base.

Since no pickling and depickling is carried out, pretanning or fulltanning may be carried out directly on the bated substrate. The pH atthe beginning of the tanning process is preferably nearly neutral tobasic, in particular in the range of 6.5 to 10, preferably 6.8 to 9, andduring the treatment gradually decreases spontaneously by a few pHunits, in particular by 1 to 4 pH units, to a nearly neutral to weaklyacidic pH range, in particular 7 to 4, preferably 6.5 to 4.5. Thetemperature is preferably in the range of 10 to 40° C., more preferably15 to 35° C. More particularly tanning is preferably begun at 10 to 30°C. more preferably 15 to 25° C., and at the end the temperature isallowed to rise by 5 to 20 degrees, preferably by 8 to 15 degrees, to 20to 40° C., preferably 25 to 40° C.

The tanning process of the invention is very simple and may be carriedout in a relatively short time, in particular within about 5 to 24hours, preferably 6 to 12 hours.

After tanning the exhausted tanning bath may be drained off and thetanned leather, skin or pelt may be rinsed or washed e.g. one to threetimes with water (e.g. 100 to 600% by weight of water, preferably 250 to400% by weight of water, the % by weight being based on the weight ofthe fleshed or (if the hide has been split) the split substrate), towhich if desired some conventional surfactants may be added, in order tofavour slippage of the grain. If desired also a biocide e.g. asmentioned above for (D), may be added during the process, e.g. into thelast washing bath, as a preserving agent for the resulting tanned hideor skin or pelt.

If desired a further non-mineral tanning agent (F), which is differentfrom (A), of anionic or/and ethylenically unsaturated character or/andcontaining groups of basic character may be applied before, after ortogether with tanning agent (A) in pre-tanning, in main tanning or infull tanning, preferably for pre-tanning before a main tanning with (A),or in combination with (A) in a main or full tanning, or/and preferablyfor a complementary tanning after a main or full tanning with (A), oreven for retanning.

(F) preferably is selected from the group consisting of

(F1) a vegetable tanning agent,(F2) a syntan,(F3) a synthetic, semisynthetic or natural resin or polymer,(F4) a tanning natural oil or modified oil, andmixtures thereof.

As vegetable tanning agents (F1) there may be employed known vegetabletanning agents, in particular pyrogallol- or pyrocatechin-based tannins,e.g. valonea, mimosa, teri, tara, oak, pinewood, sumach, quebracho andchestnut.

As syntans (F2) there may be employed known synthetic tanning agents, inparticular syntans derived from sulphonated phenols and/or naphthols,and/or sulphones or polymers of sulphones and/or sulphonated phenolsand/or sulphonated naphthols with formaldehyde or acetaldehyde andoptionally urea, among which sulphone-based products are preferred.

As synthetic or semisynthetic or natural resins or polymers (F3) theremay be employed e.g. known polyacrylates, polymethacrylates, copolymersof maleic anhydride and styrene, condensation products of formaldehydewith melamine or dicyandiamide, lignins and natural flours. Among thesynthetic or semisynthetic or natural resins or polymers (F3), those ofanionic character (e.g. polyacrylates, polymethacrylates, ligninsulphonates and copolymers of maleic anhydride and styrene) and whichare free of basic amino groups are designated herein as (F3-I).

As natural or modified oils (F4) there may be employed known naturaltriglycerides, e.g. rape seed oil, fish oils or their oxidisedderivatives, sulphated, sulphonated or oxy-sulphited fish oils, or theiroxidised derivatives, or surrogates thereof.

Tanning with (A) may be carried out as a full tanning, or as apre-tanning before a non-metal main tanning, which may be carried outwith a vegetable tanning agent or with a synthetic tanning agent otherthan (A)—e.g. as mentioned above as (F)—or also with a tanning agent (A)according to the invention, or as a main tanning after a non-metal oreven non-mineral pre-tanning (which may be vegetable or synthetic) e.g.carried out with (F) mentioned above. Where the tanning with (A) of theinvention is carried out as a main tanning subsequently to a vegetablepre-tanning or to a synthetic pre-tanning with syntans, the pH may ifrequired be adjusted to the desired value between 6 and 10, e.g. byaddition of an alkali metal carbonate, bicarbonate or formate for thetanning method of the invention.

According to a particular feature of the invention, the tanning agent(A) may be used in combination with another non-mineral tanning agent(F), preferably (F-I), (F-I) being selected from the group consisting of(F1), (F2) and (F3-I), e.g. in a weight ratio of (A) to (F-I) being offrom 0.05 to 20, more particularly from 2 to 10. The concentration ofthe combined tanning agents may be as desired for achieving a definedtanning, e.g. of from of 0.5 to 20% by weight, preferably 1 to 10% byweight, the % by weight based on the weight of the fleshed substrate.

According to a further particularly preferred feature of the invention,the substrates are first tanned in one or two stages with (A) and thenare subjected to a complementary tanning with a non-mineral tanningagent (F), which preferably is (F-II), (F-II) being selected from thegroup consisting of (F1) or (F2) and (F3). As a complementary tanningthere is intended here an additional tanning step carried out after mainor full tanning with (A), and which substantially does not modify thecharacteristic kind of properties of the leather, skin or pelt tannedwith (A), but may improve some of the typical tannage properties.Typically it is carried out with a smaller amount of the complementarytanning agent (F) compared with the amount of the employed main or fulltanning agent (A), preferably 5 to 80% by weight, preferably 10 to 60%by weight of (F), the % by weight based on the weight of the employedamount of (A). This complementary tanning may advantageously be carriedout sequentially to the tanning with (A) under temperature conditions asmentioned above, e.g. 10 to 40° C., at bath lengths preferably as usedfor tanning with (A), e.g. in the range of 40 to 200% by weight ofwater, the % by weight being based on the weight of the fleshed or (ifthe hide has been split) the split substrate, and under pH conditions asresulting from the tannage with (A), preferably after rinsing withwater, usually this pH may range in the scope of 4 to 7.

Complementary tanning with (F), preferably with (F-II), may be carriedout in the tannery directly after tanning, or even after having rinsed,dried and optionally mechanically treated the tanned leather, skin orpelt.

At the end of the tanning process, after draining off of the exhaustedtanning or complementary tanning bath, the tanned leather, skin or peltmay—if desired—be treated with one or more conventional additives e.g.one or more surfactants, preferably as mentioned above as (B), mainly(B1) or (B3), for protecting the grain from damaging friction, or/andwith a preserving agent, preferably as mentioned above as (D).

The tanned leather, skins or pelts produced according to the invention,as described above, may be further treated in conventional way, i.e. maybe drained, dried and mechanically treated as usual for storage and/orshipment.

According to another preferred feature of the invention, the substratesare first tanned in one or two stages with (A), optionally subjected tocomplementary tanning with (F) or (F-II), and then are retanned with(F).

Retanning with (F) may be carried out after having rinsed, dried andoptionally mechanically treated the tanned leather, skin or pelt e.g. inthe dye-house.

The process of the invention may be carried out in a very economic ansimple way, as a pickling and depickling may be omitted, and further thetanning itself may be carried out with a minimum quantity of water, andalso a neutralisation—as otherwise conventionally carried out e.g. aftermetal tanning—is not necessary.

By the process of the invention there may be achieved metal-free tannedleathers, skins or pelts (in particular “wet white” metal-free leathers)of outstanding properties, in particular shrinkage temperatures,softness and consistency, e.g. firm grain texture, and with satisfactoryfastnesses, especially where (A) or respectively (T) is employed for amain or full tanning. If no vegetable tanning agents at all are used orif only white to light yellowish vegetable tanning agents are also used,there may be achieved according to the invention “non-metal whitetanned” leathers, skins and pelts, in particular non-metal “wet white”leathers, of high quality and very light own colour, i.e. nearly white.Where vegetable tanning agents of brownish to reddish colour are alsoused, the shade of the resulting tanned leathers, skins and pelts willbe correspondingly slightly more brownish or reddish. Where (A) isemployed for full tanning or for pre-tanning and main tanning and isfollowed by (F), in particular (F-II), for complementary tanning,further increased shrinkage temperatures T_(s) may be achieved.

The tanned leathers, skins and pelts produced as described are suitablefor further treatment in conventional way, mainly by retanning and/orfat liquoring and optionally dyeing and/or finishing. Fat liquoring maybe carried out with known fat liquoring agents. Retanning is preferablycarried out with (F). By retanning them with (F) and fat liquoring theremay be produced upon drying high quality crust leathers. For dyeingthere may be employed known leather dyes (e.g. as defined and inparticular listed in the “Colour Index edited by Society of Dyers andColourists and American Association of Textile Chemists and Colorists”)and there may be obtained dyeings of satisfactory properties, mainlycolour penetration, colour yield and fastnesses. With those leathers,skins or pelts which are of very light own colour, i.e. are nearlywhite, as mentioned above, there may also be achieved dyeings ofdelicate shades (pastel shades) of very pleasant shade.

Conventional leather finishing agents may also be employed for finishingif desired.

Therefore, another subject of the invention is the use of the tannedleather, skins or pelts produced according to the process as describedabove, also with all its preferred embodiments, for further processingby at least one further treatment selected from the group consisting of

-   (a) retanning with a further non-mineral tanning agent (F), which is    different from the tanning agent (A),-   (b) fat-liquoring,-   (c) dyeing, and-   (d) finishing.    preferably a and b and optionally c and/or d.

In the following examples the indicated percentages are by weight; theviscosities are Brookfield rotational viscosities measured at 20 rpmwith spindle nr. 3 at 20° C. unless otherwise indicated.

EXAMPLES Example 1

500 parts of water and 500 parts of crushed ice and are charged into areactor with stirring. At this temperature 185 parts g of cyanuricchloride are added and stirring is continued for 10 to 15 minutes. Inparallel the pH of a mixture of 135 parts of 4-Aminonbenzenecarboxylicacid in 500 parts of water is adjusted to 5 with aqueous 30% by weightof sodium hydroxide solution. Then the slightly acidic solution is addedto the cyanuric chloride dispersion within 60 minutes. At this point 230parts of an aqueous 30% by weight of sodium hydroxide solution, the % byweight based on the weight of the solution, are added over the course of1-2 hours keeping the temperature below 10° C. and the pH in the rangeof 6 to 7. Near the end of the addition of the sodium hydroxide solutionthe temperature is allowed to raise to 14° C. There is obtained awhite-yellowish emulsion (Composition 1) containing the compound offormula (1).

Example 2-20

The table which follows contains compounds of formula I-III which can beprepared similarly to the method described in Example 1 by using thecorresponding starting materials.

( I-III )

Example X R1 R4 2 Cl Me

3 Cl Et ″ 4 Cl H

5 Cl Me ″ 6 Cl H

7 Cl Me ″ 8 Cl H

9 Cl Me ″ 10 Cl H

11 Cl H ″ 12 Cl H

13 Cl Me ″ 14 Cl Et ″ 15 Cl H

16 Cl Me ″ 17 Cl H

18 Cl Et ″ 19 Cl H

20 Cl H

Example 21

1,000 g of product obtained from example 1 and 400 ml ofdimethylsulfoxide are charged into a reactor with stirring and 71 g oftriethanolamine is added. The mixture is maintained under stirring at40° C. for 12-15 hours. There is obtained a white- yellowish dispersion(Composition 21) containing the compound of formula (21)

Example 22

1,000 g of the Composition 1 obtained according to Example 1 are pre-setat 20 to 25° C. and 10.2 g of disodium hydrogen phosphate, 8.7 g ofmonosodium dihydrogen phosphate and 2.0 g of NIPACIDE® BIT 20 (acommercial biocide based on 1,2-benzothiazolin-3-one of Nipa LAB's Ltd.,from Nipa Laboratorien GmbH, Germany) are added with stirring. There isobtained a white-yellowish dispersion (Composition 22).

Example 23

100 g of water are heated to 50 to 55° C. At this temperature 4 g ofhydroxyethylcellulose (having a viscosity of its 2% solution of 5,500mPa·s at 25° C. and a pH of 7.0) are added and stirring is continued for1 hour. There are obtained 104 g of hydroxyethylcellulose solution.

1,000 g of Composition 22 obtained in Example 22 are pre-set at 20 to25° C. and 103.8 g of the hydroxyethylcellulose solution is added withstirring. There is obtained a white-yellowish suspension (Composition23) having a viscosity of 1,250 mPa·s at 20° C.

Examples 24 to 61

Compositions of Examples 2 to 20 are converted like described withComposition 1 in Examples 22 and Composition 22 in Example 23 to yieldExamples 24 to 61.

Example 62

1,000 g of the Composition 21 obtained according to Example 21 arepre-set at 20 to 25° C. and 10.2 g of disodium hydrogen phosphate, 8.7 gof monosodium dihydrogen phosphate and 2.0 g of NIPACIDE® BIT 20 (acommercial biocide based on 1,2-benzothiazolin-3-one of Nipa LAB's Ltd.,from Nipa Laboratorien GmbH, Germany) are added with stirring. There isobtained a white-yellowish emulsion (Composition 62).

Example 63

100 g of water are heated to 50 to 55° C. At this temperature 4 g ofhydroxyethylcellulose (having a viscosity of its 2% solution of 5,500mPa·s at 25° C. and a pH of 7.0) are added and stirring is continued for1 hour. There are obtained 104 g of hydroxyethylcellulose solution.

1,000 g of Composition 62 obtained in Example 62 are pre-set at 20 to25° C. and 103.8 g of the hydroxyethylcellulose solution is added withstirring. There is obtained a white-yellowish suspension (Composition63).

In the following Application Examples the indicated percentages—if nototherwise indicated—refer in Application Examples A to Ea) and Ia) tothe weight of the split hide, in Application Examples Fa), Ga), Ha) andHb) to the weight of the fleshed hide, in Application Examples Fb), Gb),and Ib) to the weight of the bated hide, in Application Example Hc) tothe depickled weight of the substrate, in Application Example J to theweight of the depickled sheepskin and in Application Example K to thewet weight of the tanned leather. The shrinkage temperature T_(s) isdetermined according to standard method IUP 16/ISO 3380-2006. Where atreatment is indicated to be carried out overnight, this is of 10 to 12hours. If not otherwise indicated, pH is increased by addition ofaqueous 10% by weight of sodium formate solution, the % by weight beingbased on the weight of the solution or is lowered by addition of aqueous10% formic acid solution, the % by weight being based on the weight ofthe solution. The dyes are in commercial form blended with sodiumchloride, with a dye content of around 60%, “C.I.” stands for “ColourIndex”.

Application Example A a) Deliming and Bating:

Bovine limed hide (Swiss bull hide of the weight category 30 kg),fleshed and split to a thickness of 2.4 to 2.6 mm, is charged into adrum with 200% of water at 25° C., 0.1% of defatting agent (C₁₂₋₁₅alkanol ethoxylated with 7 mols of ethylene oxide per mol of alkanol)and 0.2% of an ammonium based deliming agent (ammonium chloride andammonium sulphate) and drummed for 20 minutes. Then the bath is drained,a fresh bath of 50% of water at 35° C., 0.1% of the above mentioneddefatting agent and 0.5% of the above mentioned ammonium based delimingagent is charged into the drum and drumming is continued for 15 minutes.A further 0.5% of ammonium based deliming agent and 0.8% of a mixture of70% boric acid and 30% mixed organic acids (adipic, glutaric andsuccinic acids in even parts) are added and drumming is carried on for90 minutes. 0.6% of Feliderm® Bate PB1 p (a pancreas enzyme based bateof Clariant, Switzerland) is added and drumming is continued for 30minutes and then the bath is drained. 300% of water is added anddrumming is carried on for 15 minutes at 35° C. then the bath isdrained.

b) Tanning:

A fresh bath of 50% water at 20° C. and 10% of Composition 22 accordingto Example 22 is added and drumming is carried on for 60 minutes, thenthe bath is heated during 120 minutes to 30° C. and drumming iscontinued overnight at 30-35° C. Then the bath is drained. 300% of waterat 20° C. is added and drumming is continued for 30 minutes and then thebath is drained and the leather discharged and horsed up.

If desired 0.2% of Preventol® WB (a biocide of Bayer, Germany) is addedto the last 300% of water.

The so obtained leather is then sammied and shaved to 2.0 to 2.2 mm.

Application Example B

The procedure described in Application Example A is repeated up to thetanning treatment with Composition 2 and drumming overnight at 30 to 35°C.

Complementary Tanning:

After drumming overnight 1% of a syntan based on sulphomethylateddihydroxydiphenylsulphone reacted with formaldehyde is added forcomplementary tanning and drumming is continued for 120 minutes and thenthe bath is drained. 300% of water at 20° C. is added and drumming iscontinued for 30 minutes and then the bath is drained and the leatherdischarged and horsed up. The so obtained leather is then sammied andshaved to 2.0 to 2.2 mm.

If desired 0.2% of Preventol® WB is added to the last 300% of water.

Application Example C

The procedure described in Application Example C is repeated up to thetanning treatment with Composition 3 and drumming overnight.

Complementary Tanning:

After drumming overnight 1% of syntan based on sulphomethylateddihydroxydiphenylsulphone reacted with formaldehyde is added forcomplementary tanning and drumming is continued for 120 minutes and thenthe bath is drained. 300% of water at 20° C. is added and drumming iscontinued for 30 minutes and then the bath is drained and the leatherdischarged and horsed up. The so obtained leather is then sammied andshaved to 2.0 to 2.2 mm.

Application Example D a) Deliming and Bating:

Bovine limed hide (Spanish bull hide of the weight category 30 kg),fleshed and not split is charged into a drum with 200% of water at 25°C., 0.1% of defatting agent (C₁₂₋₁₅ alkanol ethoxylated with 7 mols ofethylene oxide per mol of alkanol) and 0.2% of an ammonium baseddeliming agent (ammonium chloride and ammonium sulphate) and drummed for20 minutes. Then the bath is drained, a fresh bath of 50% of water at35° C., 0.1% of the above mentioned defatting agent and 0.5% of theabove mentioned ammonium based deliming agent is charged into the drumand drumming is continued for 15 minutes. A further 0.5% of ammoniumbased deliming agent and 0.8% of a mixture of 70% boric acid and 30%mixed organic acids (adipic, glutaric and succinic acids in even parts)are added and drumming is carried on for 90 minutes. The pH is 7.8 andthe cross section of the hide is colourless to phenolphthalein indicatorsolution. 0.6% of Feliderm® Bate PB1 p is added and drumming iscontinued for 30 minutes and then the bath is drained. 300% of water isadded and drumming is carried on for 15 minutes at 35° C. then the bathis drained.

b) Tanning:

A fresh bath of 50% water at 20° C. is added. The pH is measured andadjusted to 8. 15% of Composition 23 according to Example 23 is addedand drumming is carried on for 60 minutes, then the bath is heated to30° C. and drumming is continued overnight at 30-35° C. Then the bath isdrained off. 300% of water at 20° C. is added and drumming is continuedfor 20 minutes.

If desired 0.2% of Preventol® WB is added to the last 300% of water.

Then the bath is drained off, the leather is discharged and horsed up.The so obtained leather is then sammied and split and shaved to 1.4 to1.6 mm.

Application Example E a) Deliming and Bating:

Bovine limed hide (Spanish bull hide of the weight category 30 kg),fleshed and not split is charged into a drum with 200% of water at 25°C., 0.1% of defatting agent (C₁₂₋₁₅ alkanol ethoxylated with 7 mols ofethylene oxide per mol of alkanol) and 0.2% of an ammonium baseddeliming agent (ammonium chloride and ammonium sulphate) and drummed for20 minutes. Then the bath is drained, a fresh bath of 50% of water at35° C., 0.1% of the above mentioned defatting agent and 0.5% of theabove mentioned ammonium based deliming agent is charged into the drumand drumming is continued for 15 minutes. A further 0.5% of ammoniumbased deliming agent and 0.8% of a mixture of 70% boric acid and 30%mixed organic acids (adipic, glutaric and succinic acids in even parts)are added and drumming is carried on for 90 minutes. The pH is 7.8 andthe cross section of the hide is colourless to phenolphthalein indicatorsolution. 0.6% of Feliderm® Bate PB1 p is added and drumming iscontinued for 30 minutes and then the bath is drained. 300% of water isadded and drumming is carried on for 15 minutes at 35° C. then the bathis drained.

b) Pickling and Depickling:

70% of water at 20° C. and 7% of sodium chloride are added and drummingis carried on for 10 minutes. 0.8% of formic acid diluted 1:3 with wateris added and drumming is continued for 30 minutes, then 1.5% ofsulphuric acid diluted 1:10 with water is added and drumming iscontinued for 3 hours, then the pickle bath with the hide are allowed todwell overnight with intermittent drumming of 5 minutes every hour.After this treatment the pH is 2.7 to 2.9. The bath is drained the hideis discharged and sammied. The drum is charged with 100% of water at 20°C. and 10% of sodium chloride, the drum is switched on and drumming iscontinued for 10 minutes, then the hide is charged into the drum anddrumming is carried on for 30 minutes, then 1% of sodium bicarbonate isadded and drumming is continued for 120 minutes, then the drum isstopped and the depickling bath with the hide are allowed to dwellovernight. The pH is about 8. Then the bath is drained off and the hideis rinsed with 200% of water at 20° C. for 15 minutes and then the bathis drained off.

c) Tanning

50% of water is added and the pH is adjusted to 8 by addition of 0.5% ofsodium bicarbonate and 0.5% of sodium formate. The pH of the crosssection of the hide is 8 (determined with phenolphthalein indicator).15% of Composition 1 according to Example 1 is added and drumming iscarried on for 1 hour, then the bath is heated to 35° C. and drumming iscontinued overnight at 35° C. Then the bath is drained off. 300% ofwater at 20° C. are added and drumming is continued for 20 minutes.

If desired 0.2% of Preventol® WB is added to the last 300% of water.

Then the bath is drained off, the leather is discharged and horsed up.The so obtained leather is then sammied and split and shaved to 1.4 to1.6 mm.

Application Example F a) Deliming and Bating:

Bovine limed hide (Spanish bull hide of the weight category 30 kg),fleshed and split to a thickness of 2.4 to 2.5 mm, is charged into adrum with 200% of water at 25° C., 0.1% of defatting agent (C₁₂₋₁₅alkanol ethoxylated with 7 mols of ethylene oxide per mol of alkanol)and 0.2% of an ammonium, based deliming agent (ammonium chloride andammonium sulphate) and drummed for 20 minutes. Then the bath is drained,a fresh bath of 50% of water at 35° C., 0.1% of the above mentioneddefatting agent and 0.5% of the above mentioned ammonium based delimingagent is charged into the drum and drumming is continued for 15 minutes.A further 0.5% of ammonium based deliming agent and 0.8% of a mixture of70% boric acid and 30% mixed organic acids (adipic, glutaric andsuccinic acids in even parts) are added and drumming is carried on for90 minutes. The pH is 7.8 and the cross section of the hide iscolourless to phenolphthalein indicator solution. 0.6% of Feliderm® BatePB1 p (a pancreas enzyme based bate of Clariant, Switzerland) is addedand drumming is continued for 30 minutes and then the bath is drained.300% of water is added and drumming is carried on for 15 minutes at 35°C. then the bath is drained.

b) Tanning:

A fresh bath of 50% water at 20° C. is added. The pH is 8. 10% ofComposition 1 according to Example 1 is added and drumming is carried onfor 60 minutes, then the bath is heated during 120 minutes to 30° C. anddrumming is continued overnight at 30 to 35° C.

c) Complementary Tanning:

After drumming overnight 2% of Tara (commercial vegetable tanning agent,which is an aqueous composition of 50% by weight concentration, based onthe weight of the composition, of an extract of the pods of CaesalpiniaSpinosa) is added and drumming is continued for 3 hours at 35° C. Thenthe bath is drained off. 300% of water at 20° C. is added and drummingis continued for 30 minutes. Then the bath is drained off, the leatheris discharged and horsed up. The so obtained leather is then sammied andshaved to 2.0 to 2.2 mm.

Application Example G a) Depickling:

Bated and pickled sheepskins are given into a drum with 100% of water at20° C. and 10% of sodium chloride and drummed for 10 minutes. 1% ofsodium bicarbonate and 1% of sodium carbonate are added and drumming iscontinued for 10 minutes then the bath is drained off. A fresh bath of150% of water and 2% of defatting agent (C₁₂₋₁₅ alkanol ethoxylated with7 mols of ethylene oxide per mol of alkanol) is added and drumming iscontinued for 1 hour, then the bath is drained off and a fresh bath of150% of water and 2% of the defatting agent is added and drumming iscontinued for 1 further hour, then the bath is drained off. The skinsare washed twice with each time 300% of water at 20° C., then the bathis drained off. The pH is 8.

b) Tanning:

50% of water at 20° C. and 20% of Composition 23 are added and drummingis continued for 2 hours then the temperature is raised slowly to 35°C., and drumming is continued at 35° C. overnight. The pH is 5.5. Afresh bath of 300% of water at 20° C. is added and after drumming for 30minutes the bath is drained off, the leather is discharged, horsed upand sammied.

Application Example H

The leather obtained in Application Example D is retanned, fatliquoredand dyed as follows:

The leather is charged into the drum, 200% of water at 25° C. and then0.3% of defatting agent (C₁₂₋₁₅ alkanol ethoxylated with 7 mols ofethylene oxide per mol of alkanol) are added, the drum is switched onand drumming is carried on for 20 minutes. 0.5% acetic acid, diluted1:10 is added and drumming is continued for 20 minutes. The pH is 4.5and the cross section of the leather turns green by testing withBromocresol Green indicator. The bath is drained off. 100% of water at25° C. and then 1.6% of fatliquoring agent (oxy-sulphited fish oil) areadded and drumming is continued for 20 minutes. 5% of a retanning syntanbased on sulphomethylated dihydroxydiphenylsulphone reacted withformaldehyde and 5% of a phenolic syntan (reaction product ofsulphonated phenol with formaldehyde and urea) are added and drumming iscarried on for 2 hours. The bath is allowed to dwell overnight withintermittent drumming for 5 minutes every hour, then 0.5% of formic aciddiluted 1:10 is added and drumming is carried on for 20 minutes, thenthe bath is drained off and the leather is washed with 200% of water.The bath is drained off. 100% of water at 50° C. is added followed by 5%of fat liquoring agents (3.5% alkylsulphosuccinate and 1.5%oxy-sulphited fish oil) and drumming is continued for 1 hour. Afteraddition of 0.5% of formic acid drumming is carried on for 20 minutesand then the bath is drained off. The leather is rinsed for 5 minuteswith 200% of water at 20° C. The bath is then drained off. 50% of waterat 20° C. and 5% of the black dye C.I. Acid Black 210 is added anddrumming is continued for 1 hour, then 200% of water at 50° C. and 1% offormic acid are added and drumming is continued for 10 minutes, then afurther 1% of formic acid is added and drumming is carried on for 20minutes, then the bath is drained off. 200% of water at 20° C. and 1.5%of a cationic surfactant2-(8-heptadecenyl)-4,5-dihydro-1,3-bis(2-hydroxyethyl)-1H-imidazoliumchloride are added and drumming is carried on for 15 minutes, then thebath is drained off and the leather is discharged. After 24 hours it isset out, vacuum dried at 60° C. during 2 minutes, dried hanging andstaked. There is obtained a black dyed leather of satisfactoryproperties.

By employing 2% the brown dye C.I. Acid Brown 237 instead of the 5% ofthe black dye C.I. Acid Black 210, there is obtained a brown dyedleather of satisfactory properties.

Analogously as the leather from Application Example D also the leathersobtained according to each of Application Examples A to C, E to G areretanned, fat liquored and dyed according to the procedure described inApplication Example H.

In the above Application Examples there are obtained leathers ofsatisfactory commercial grade in particular with satisfactory graintightness, texture consistency (e.g. as resulting from some typicalproperties such as tensile strength, tear load and stitch tearresistance), softness, fastnesses and general appearance. In the dyeingexamples there are further obtained dyed leathers of satisfactoryproperties in particular shade, dye penetration and colour yield, andfastnesses of the dyeing.

Application Example I a) Deliming and Bating:

Bovine limed hide (Spanish bull hide of the weight category 30 kg),fleshed and split to a thickness of 2.4 to 2.5 mm, is charged into adrum with 200% of water at 25° C., 0.1% of defatting agent (C₁₂₋₁₅alkanol ethoxylated with 7 mols of ethylene oxide per mol of alkanol)and 0.2% of an ammonium based deliming agent (ammonium chloride andammonium sulphate) and drummed for 20 minutes. Then the bath is drained,a fresh bath of 50% of water at 35° C., 0.1% of the above mentioneddefatting agent and 0.5% of the above mentioned ammonium based delimingagent is charged into the drum and drumming is continued for 15 minutes.A further 0.5% of ammonium based deliming agent and 0.8% of a mixture of70% boric acid and 30% mixed organic acids (adipic, glutaric andsuccinic acids in even parts) are added and drumming is carried on for90 minutes. The pH is 7.8 and the cross section of the hide iscolourless to phenolphthalein indicator solution. 0.8% of Feliderm® BatePB1 p (a pancreas enzyme based bate of Clariant, Switzerland) is addedand drumming is continued for 30 minutes and then the bath is drained.300% of water is added and drumming is carried on for 15 minutes at 35°C. then the bath is drained.

b) Tanning:

A fresh bath of 50% water at 20° C. is added. The pH is 8. 20% ofComposition 63 according to Example 63 is added and drumming is carriedon for 60 minutes, then the bath is heated during 120 minutes to 30° C.and drumming is continued overnight at 30 to 35° C.

c) Complementary Tanning:

After drumming overnight 2% of Tara (commercial vegetable tanning agent,which is an aqueous composition of 50% by weight concentration, based onthe weight of the composition, of an extract of the pods of CaesalpiniaSpinosa) is added and drumming is continued for 3 hours at 35° C. Thenthe bath is drained off. 300% of water at 20° C. is added and drummingis continued for 30 minutes. Then the bath is drained off, the leatheris discharged and horsed up. The so obtained leather is then sammied andshaved to 2.0 to 2.2 mm. If desired 0.2% of Preventol® WB is added tothe last 300% of water.

1. A process for the production of tanned leather, skin or pelt bynon-metal tanning, comprising the step of tanning a bated hide, skin orpelt with a tanning agent (A), the tanning agent (A) being at least onecompound of formula (I)

X is fluorine or chlorine (³⁰NR₃)₀₋₁ or a combination thereof, wherein Ris a substituted C₁ to C₆ alkyl group, an unsubstituted C₁ C₆ alkylgroup, an unsubstituted C₆ C₁₀ aryl group, a substituted C₆ C₁₀ arylgroup or a C₅ C₆ heteroaryl group. R1 is hydrogen, C₁₋₈-alkyl or analkyleneoxy radical of formula (Ia),—(—C₂₋₃ alkylene—O—)_(q)—H  (Ia) R2 is hydrogen, hydroxy, C₁₋₄-alkyl orC₁₋₄-alkoxy, m is 1 or 2, n is 0 to 2, q is from 1 to 10, M is hydrogen,an alkali metal cation or an ammonium cation, the ammonium cation beinga protonated tertiary amine or a quaternary ammonium cation, in atanning bath, the tanning bath having a pH of from 6 to 10 at thebeginning of tanning step, wherein the bated hide or skin or pelt issubjected to tanning with (A) without previous pickling.
 2. A processaccording to claim 1, wherein the tanning agent (A) is an aqueouscomposition (T) free of metal compounds of tanning activity.
 3. Aprocess according to claim 1, wherein the composition (T) is acomposition (T1), the composition (T1) further comprising a surfactant(B) a buffer (C₁) or a mixture thereof to keep an acidic to neutral pH.4. A process according to claim 3, wherein the composition (T1) furthercomprises an agent (D) to protect against the damaging action ofmicroorganisms, a polysaccharide-based thickener (E) or a mixturethereof.
 5. A process according to claim 1, wherein aqueous composition(T1) comprises a thickener (E).
 6. A process according to claim 1,wherein the tanning bath comprises a buffer (C2) to achieve a nearlyneutral to basic pH at the beginning of the tanning step.
 7. A processaccording to claim 1, wherein the tanning step with the tanning agent(A) is a pre-tanning, a main tanning or a full tanning or a pretanningand a main tanning.
 8. A process according to claim 7, wherein anon-mineral tanning agent (F), which is different from the tanning agent(A), is used before, after or together with tanning agent (A) inpre-tanning, in main tanning or in full tanning, or in combination withtanning agent (A) in full tanning.
 9. A process according to claim 8,wherein the non-mineral tanning agent (F) is selected from the groupconsisting of (F1) a vegetable tanning agent, (F2) a syntan, (F3) asynthetic, semisynthetic or natural resin or polymer, (F4) a tanningnatural oil or modified oil, and mixtures thereof.
 10. A processaccording to claim 8, wherein the leather, skin or pelt is tanned withtanning agent (A) in a main or full tanning and then subjected to acomplementary tanning with the non-mineral tanning agent (F).
 11. Aprocess according to claim 8, wherein the non-mineral tanning agent (F)is employed in a smaller amount compared with the amount of the tanningagent (A).
 12. A tanning agent (A) in a tanning process comprising atleast one compound of formula (I),

wherein X is a fluorine or chlorine (³⁰NR₃)₀₋₁ or a combination thereof,wherein R is a substituted C₁ to C₆ alkyl group, an unsubstituted C₁ toC₆ alky group, an unsubstituted C₆ C₁₀ aryl group, a substituted C₆ toC₁₀ aryl group or a C₅ to C₆ heteroaryl group. R1 is hydrogen,C₁₋₈-alkyl or an alkyleneoxy radical of formula (Ia),—(—C₂₋₃ alkylene—O—)_(q)—H  (Ia) R2 is hydrogen, hydroxy, C₁₋₄-alkyl orC₁₋₄-alkoxy, m is 1 or 2, n is 0 to 2, q is of from 1 to 10, M ishydrogen, an alkali metal cation or an ammonium cation, the ammoniumcation being a protonated tertiary amine or a quaternary ammoniumcation.
 13. A process according to claim 1, further comprising at leastone further treatment selected from the group consisting of (a)retanning with a non-mineral tanning agent (F), which is different fromthe tanning agent (A), (b) fat-liquoring, (c) dyeing, and (d) finishing.14. A process according to claim 1, further comprising a furthertreatment comprising retanning with a non-mineral tanning agent (F). 15.A process as according to claim 1, further comprising a furthertreatment comprising retanning with non-mineral tanning agent (F),fat-liquoring and optionally dyeing, finishing or a mixture thereof. 16.Tanned leather, skin or pelt made by the process according to claim 1.